Method for controlling unwanted vegetation



United States Patent 3,490,894 METHOD FOR CONTROLLING UNWANTEDVEGETATION Everett E. Gilbert, Morris Township, Morris County, NJ.,assignor to Allied Chemical Corporation, New York, N.Y., a corporationof New York No Drawing. Original application Aug. 11, 1965, Ser. N0-

478,984, now Patent No. 3,396,227, dated Aug. 6, 1968. Divided and thisapplication May 20, 1968, Ser. No.

In. or. A01n 9/24 US. Cl. 71-122 9 Claims ABSTRACT OF THE DISCLOSUREPesticidal compositions and method for killing weeds with dihydricfluoroalcohols and their alkali metal and ammonium salts.

This application is a division of my application Ser. No. 478,984 filedAug. 11, 1965, now US. Patent No. 3,396,227.

This invention relates to pesticidal compositions and to a method forcontrolling various biological pests, including insects, mites,nematodes and unwanted vegetation by the application to the pests ortheir hosts of certain dihydric fiuoroalcohols prepared by the reactionof perhaloacetones with alpha olefins at a 2:1 molar ratio.

I have found the resulting compounds and certain of their monoanddialkali metal and monoand diammonium salts are active preandpost-emergence herbicides, as well as insecticides, miticides andnematocides.

Compounds suitable for use as pesticides according to my invention arethe dihydric fluoroalcohols shown below and the monoand dialkali metaland monoand diammonium salts of those compounds wherein all the X groupsare fluorine.

In the above formula R is a member selected from the group consisting ofphenyl and lower alkyl groups of 1 to 3 carbon atoms, and X is a memberselected from the group consisting of fluorine and chlorine.

The fluoroalcohols used in my invention can be prepared by reacting twomoles of perhaloacetone with one mole of an alpha alkene such asisobutylene and alpha methyl styrene, as described in copendingapplication, Ser. No. 157,270, of Morton H. Litt and George J. Schmitt,filed Dec. 5, 1961, now US. Patent No. 3,324,187 and shown in theequation below.

C F X H CCO H H20 0 F X (I!) C F 2X R 20 0 R C C F zX H3 0 F 2X H2 O OHC FzX alkene perhaloacetone dihydric fiuoroalcohol When R in the alkeneshown above is a lower alkyl radical, I have found that minorproportions of the structural isomers shown below are formed in amountsranging from about 25% to 35% of the total yield in 3,490,894 PatentedJan. 20, 1970 When reference is made herein to the1,3-bis(1,3-hexahalo-2-hydroxy-2-propyl)-2-alkyl-1-propenes, the term isintended to include mixtures of the stated compound with minorproportions of its double bond-variant isomer as described.

The resulting dihydric fluoroalcohols are solids only slightly solublein water.

The monoalkali metal and ammonium salts of the above fluoroalcohols, ofwhich the alkali metal salts are water-soluble solids, the ammonium saltis water insoluble, can be prepared from those of the above alcohols inwhich all the X members are fluorine, by simply mixing the alcohols withan aqueous alkali metal hydroxide or anhydrous ammonia.

The dialkali metal and diammonium salts can also be prepared, butrequire the use of large excesses of alkali and long reaction times.

Among the compounds useful as pesticides according to my invention arethe following I. 1,3-bis (1,3-dich1orotetratluoro-2-hydroxy-2-propyl)-2- phenyl-l-propene II. 1,3-bis(hexafluoro-2-hydroxy-2-propy1)-2-pheny1-1-propene CFa III. 13bis(hexafluoro-2-hydroxy-2-propyl) -2-phenyl-1- propene-monosodium salt IV.1,3-b is (hexafluoro-2-hydroxy-2-propyl -2-methyl-1-propene and minoramounts of 1,3-bis(hexafiuoro 2 hydroxy-2' propyl) -2-methy1ene propaneon. or, on H =co-on H2O-COH CFa CF GF3 and 11,0:0 3 z 1120-0-011 a. o onV. 1,3-bis (hexafiuor0-2-hydroxy-2-propy1) -2-methy1-1- propenemonosodium salt VI. 1,3-bis(1,3-dichlorotetrafluoro 2hydroxy-2-propyl)-2- methyl-l-propene with minor amounts of1,3-(1,3-dich10rotetrafluoro-2-hydroxy-2-propy1)-2-methylene propaneVII. Disodium salt of 1,3-bis(hexafiuoro-2-hydroxy-2-propyl)-2-methyl-1-propene The compounds described herein have strongbiocidal activity in a number of important fields to combat or controlsuch pests by contacting such pests either directly or by application ofthe compounds to the environment or habitat or host of the pest. Theycan be employed as herbicides in combating unwanted vegetation in eitherpre-emergence or post-emergence application to soils and or plants.

In the insecticidal field, control of many noxious pests can be effectedby contacting the pests or their environment, their food or the host,such as insect infested plants, soils, etc., with the dihydricfluoroalcohol compounds and salts of the perfluoro compounds. Among theinsects which can be controlled by the process of my invention areMexican bean beetles (Epilachna varivestis), southern armyworms(Prodenia eridania), pea aphids (Macrasiphum pz'si), two-spotted spidermites (Tetranychus te- Iarius), house flies (Musca domestica) and manyothers, which are affected thereby in either adult, nymph, larval or eggfor-m. Nematode control can also be effected by the process of myinvention.

When reference is made herein to contacting biological pests with thecompound of the invention, it is to be understood to include not onlydirect contacting, but also such contact achieved through treatment ofthe environment, habitat, food or host of such pests.

Application of the toxicant can be made in conventional manner, inadmixture with a carrier. Usually the toxic compounds are mixed with atleast one diluent, either solid or liquid, and are applied to the pestor its host, for example, as a finely divided dust, coarse granules orpellets, solvent solutions or aqueous sprays. The alcohols of myinvention and the ammonium salts which are relatively insoluble in watercan be prepared in the form of aqueous dispersions by dissolving thealcohol in a solvent such as xylene and dispersing the solution in waterwith the aid of anionic, cationic, or non-ionic wetting, dispersing, oremulsifying agents. In the case of the highly watersoluble alkali metalsalts of the alcohols from hexafluoroacetone, these compounds can bedissolved in water alone and applied as water solutions, as well asbeing applied in dispersions if desired. Concentrations of toxicant willdepend on the sensitivity of the pest organisms to be controlled.Usually concentrations between about .03% and about 3.0% are sufficient.

Dusts, granules, pellets and wettable powders can also be used inapplying the dihydric fluoroalcohol compounds or their salts accordingto my invention. For the preparation of dusts the alcohol or theappropriate salt thereof may be mixed in finely divided solid form withsuitable powders including finely divided dry solid talc, clays such asattapulgite, kaolin, or fullers earth, wood flour, or other inert solidcarriers of the type commonly employed in formulating pesticidal powdercompositions. These powders may be granulated or pelleted; or solutionsor the dihydric fluoroalcohol carbonates may be impregnated intogranular or pelleted carriers of mineral and vegetable origin. Wettablepowder formulations, suitable for dispersing in water and applying thewater dispersion to the soil, plants or insects, etc., are prepared byincorporating in any of the finely divided powders, small amounts ofsurface active materials, for example, about 1% to about 5% by weight,which serve to maintain the finely powdered composition dispersed inwater with which it is mixed.

long chain aliphatic carboxylic acids, sulfonates of the aromatic orlong chain aliphatic hydrocarbons, such as sodium alkyl sulfates andsulfonates, alkyl aryl sulfonate salts, sulfonates of glycerides andtheir fatty acids and sulfonates of derivatives of fatty acid esters.

EXAMPLE 1 Preparation of monosodium salt of 1,3-bis(hexafluoro-2-hydroxy-Z-propyl) -2-methyl-1-propene."

(A) Eighty grams (0.206 mole) of 1,3-bis(hexafluoro-2-hydroxy-2-propyl)-2-rnethyl-1-propene prepared by reaction ofisobutylene and hexafluoroacetone at 1:2 molar ratio was mixed with 42ml. (0.21 mole) of 5 N aqueous sodium hydroxide and the mixture washeated at the boiling point for 15 minutes producing a clear solution.The reaction mixture was vacuum dried for 5 days resulting in a white,free-flowing powder melting at 55-58 C. The yield was grams whichcorresponds to a theoretical yield for the monohydrated, monosodiumsalt.

Analytical data are shown below in comparison to calculated data for themono and disodium salts with l and 2 molecules of water of hydration.

Calculated O H Na Mono Na Salt:

Anyhdrous 29. 2 1. 7 5. 5

(B) Example 1A was repeated except that an excess of sodium hydroxidewas used, i.e., 20 ml. of 1 N aqueous NaOH equivalent to 0.020 mole,with 2.0 grams, 0.00515 mole of the isobutylene hexafluoroacetonereaction product. The reactants were refluxed for 1 hour and were thenallowed to cool to room temperature, i.e., about 25 C., extracted with50 ml. ethyl ether, and evaporated to dryness. The solid wasrecrystallized once from benzene and dried for 24 hours at 60 C. invacuo. They melted at 226230 C. Elemental analysis showed. Found: C,29.0; H, 2.5; Na, 5.7.

(C) A third sodium salt was prepared by refluxing the reaction productof isobutylene and hexafluoroacetone of Example l-A with an excess of 4N aqueous sodium hydroxide for 24 hours, cooling, and separating theresulting crystals and drying the crystals to constant weight in vacuo,at C. The resulting compound melted at 230235 C. and had the followingelemental analysis. Found: C, 29.3; H, 2.3; Na, 6.0.

EXAMPLE 2 Preparation of disodium salt The 1:2 molar adduct ofisobutylene and hexafluoroacetone was heated to boiling with a tenfoldmolar excess of 10 N aqueous NaOH and was then cooled tocrystallization. The resulting crystals were separated by filtration andrecrystallized twice from toluene. A second sample was similarlyprepared except that refluxing and stirring was continued overnight.

Both samples melted over the range 103-200 C. Both samples were analyzedfor carbon, hydrogen, sodium and water with the results shown belowindicating the product to be the disodium dihydrate.

Found: C, 25.64; H, 2.34; Na, 8.3.

6 EXAMPLE 3 equivalent to 16, 8 or 4 pounds per acre, and held forPreparation of sodium salt of 1,3-bis(hexafiuoro-2- s g' gg observammperiod after whlch they hydroxy'zp top Y1) 'z-p henyl'l'prol? me In boththe pre-emergence and post-emergence tests, Twenty-seven grams (0.06mole) of 1,3-b1s(hexafluor0- similarly seeded but untreated flats wereheld for com- 2-hydroxy-2-propyl)-2-phenyl-1-propene produced by re- 5parison. The response of the test plant to the toxicant was action ofa-methyl styrene and hexafiuoroacetone in 1:2 measured by injury rating(IR) on a scale of to 10; molar ratio, were mixed with 2.6 grams (0.065mole) of 0 indicating no injury, 10 indicating complete kill of the Naqueous sodium hydroxide in ml. of Water. The test plants. Percentmortality (PK), a calculated index, mixture was warmed for minutes on ahot plate. The is obtained by comparing the mortality in the toxicantresulting solution was dried 5 days in vacuo and yielded 10 treatedflats with that in the untreated flats. Results of 29 grams of themonosodium salt as a dry white powder both pre-emergence andpost-emergence tests are shown corresponding to a 100% theoretical yieldof monoin Table II.

TABLE II Pre-ernergence Lbs. Corn Cotton Wheat Soybeans Rye Grass RapeCompound No. A 3; IR PK IR PK IR PK IR PK IR PK IR PK Post-emergence (IRCrops Weeds Crops and Weeds Corn Cotton Wheat Soybeans Av Rye Grass RapeAv. Average 1 IR=Injury Rating; 0=No Injury, 10=Complete Kill. 2PK=Percent Kill.

hydrated monosodium salt, which was completely water- It will be notedfrom Table II that the compounds of soluble. the invention showexcellent selective pre-emergence kill EXAMPLE 4 of broadleaf weeds, asexemplified by rape, with little or no crop injury. Post-emergence testsshowed good to exl I w The compounds hstgd m Tab 6 ere tested as precellent nonselectrve contact activity, especially on broademergence andpost-emergence herbicides in Standard Macroscreening greenhouse testsaccording to the method leaf Plantsof Shaw and Swanson described inWeeds, volume 1, EXAMPLE 5 Pages Four compounds were subjected topro-emergence test TABLE 1 against crabgrass and Johnson grass with thetoxicant applied at the rate of 16 pounds per acre, using the methodCompounds tested as weed klllers described in Example 4 above andobserved for injury (I)1,3-bis(l,3-dichlorotetrafluoro-2-hydroxy-2-propyl)- rating with resultsshown in Table III below. The com- Z-phenyl-l-propene. pounds testedwere Nos. H, IV, V and VII identified in (II)1,3-bis(hexafluoro-2-hydroxy-2-propyl)-2-pheny1-1- Table I above.

Propene- TABLE IIL-PRE-EMERGENOE TESTS ON GRASSES (HI) Monosodium saltof 1,3-bis(hexafluoro-Z-hydroxy- Z-propyl) -2-phenyl-1-propene. Inlurymung (IV) 1,3-bis(hexafluoro-2-hydroxy-2-propyl)-2-methyl- Compound No.Crabgrass .Iohnson Grass l-propene. 5 8 (V) Monosodium salt of1,3-bis(hexafluoro-Z-hydroxy- 9 10 2-propyl) -2-methy1- l-propene. g

(VI) l,3-bis(1,3-dichlorotetrafluoro-Z-hydroxy-Z-propyl)- 0 The abovetests indicate good to excellent control of (VII) Dlsodmm Salt of13'bls(hexafluoroz'hydroxy'z' crabgrass and Johnson grass by theindicated compounds.

propyl) -2-methyl-1-propene.

In the pre-emergence tests, the toxicant, dispersed in a EXAMPLE 6liquid such as acetone 01' water, was sprayed, within one The compoundslisted below were tested for insecticidal day after seeding, onto seededflats containing test crop activity against one or more of the pests,Mexican bean seed species and test weed seed species, at a volume ofbeetles, pea aphids, southern armyworms and two-spotted spray equal to80 gallons of spray per acre and at conspider mites, by preparingsuspensions in acetone of the centrations of toxicant per acre of 16, 8,or 4 pounds per compounds and adjusting them to concentrations of 2acre. Immediately after spraying, the test flats were subpounds oftoxicant per 100 gallons of suspension. Comirrigated and the neededmoisture maintained during the pound I below was also tested atconcentrations of lb. following 16-day test period, during which theflats were per 100 gallons. The suspensions were then sprayed in theheld in the greenhouse for observation, and were then standard manneronto the leaves of the bean plants, 2 rated as described hereinafter. Inthe post-emergence tests, seconds on the upper surface and 5 seconds onthe under flats with crop and weed seedlings were treated 8 to 10surface. After spraying, the deposits were allowed to dry days afterseeding with the indicated toxicant at a rate on the plants and theparticular pests being tested were 7 confined in cages on the treatedleaves. Three days after treatment the plants were observed andmortality records taken in percent kill of the pest.

The compounds thus tested were:

8 EXAMPLE 8 The compound listed below were tested as toxicants againsthouseflies (M urea domestica) by preparing a bait mixture of powderedmilk, granulated sugar and powdered (I)1,3-bis(l,3-dichlorotetrafluoro-2-hydroxy2-propyl)- egg and addingthereto solutions or suspensions of the 2-phenyl-l-propene. toxicant inamounts of 0.5% or less of the bait. The bait (II)l,3-bis(hexafiuoro-Z-hydroxy-2-propyl)-2-phenyl-lis then allowed to dryand is repulverized. The treated propene. food is then placed inemergence cages containing 50 fly (III) Monosodium salt of1,3-bis(hexafluoro-Z-hydroxypupae. Cages containing untreated food wereused as 2-propyl)-2-phenyl-l-propene. 10 checks. Examinations of eachcage were made periodically (IV) 1,3-bis(hexafluoro-2-hydroxy-2-propyl)-2-methyl-lto determine emergence,condition of fllies and acute propene. toxicity. Nine days after startof test, .oviposition medium (V) Monosodium salt ofl,3-bis(hexafluoro-2-hydroxy-2- was placed in each cage, and on thefollowing day the propyl)-2-methyl-1-propene. medium was examined foreggs, and if none were present, (VI)l,3-bis(1,3-dichlorotetrafluoro-2-hydroxy-2propyl) the medium wasmoistened and examined daily until ovi- 2-methyl-1-propene. positionocurred or all adults were dead. Egg viability was Results of the testsare shown in Table IV below determined by inspeqting i medlum for growmglarvae 2 to 3 "days after oviposition. TABLE IV Results of these testson compounds:

Percent Km (I) 1,3-bis( 1,3-dichlorotetrafluoro-2-hydroxy-2-propyl) -2-Bean Pea 802E113}; Two-spotp heny1-1:prop ene; Compound Lbs. per beetleaphid worm ted spider (H) y y' p py p y No. 100 gals. larvae adultslarvae mite propene;

2 100 100 100 100 (III) Monosodium salt of 1,3-bis(hexafiuoro-Z-hydroxy- 0 38 3g 2-propyl) -2-phenyl-1-propene; 2 80 100(IV) 1,3-bis (hexafluoro-2-hydroxy-2-propyl)-2-methyl-1- 2 100 100propene. 2 100 97 2 100 100 (V) Monosodium salt of1,3-b1s(hexafiuoro-Z-hydroxy-Z- 3O propyl -2-methyl-l-propene; andEXAMPLE 7 (VI) 1,3 bis(1,3 dichlorotetrafluoro Z-hydroxy 2- Thecompounds listed below were tested for nematopropyl)'z'methyl'l'pmpenecidal activity by formulating solutions of the toxicant as are shown inTable VI below.

TABLE VI Percent Kill Larvae No. Flies 7 Days 8 Days 9 Days 10 Days EggsLaid Condition None. D0.

Normal Do. V None Check none Normal acetone solutions (4.8 grams/100ml.) and diluting the solutions with water to 0.1% (1,000 parts permillion) of toxicant. Into each of three small petri dishes were placed5 ml. of the toxicant solution and approximately 100 nematode worms wereplaced in each solution. The dishes were held in a dark room attemperatures of 75 to 80 F. Observations of the worms after 1, 2 and 3days were made to determine the percent mortality of the worms.

In the above test, compounds III, the monosodium salt of 1,3bis(hexafluoro 2-hydroxy-2-propyl)-2-phenyl-1- propene; V, themonosodium salt of 1,3-bis (hexafluoro-2hydroxy-2-propyl)-2-methyl-1-propene; IV, 1,3-bis(hexafluoro 2 hydroxy 2propyl) 2. methyl 1 propene and VI, 1,3 bis(1,3dichlorotetrafluoro-Z-hydoxy-2-propyl)-2-methyl-1-propene gave resultsshown in Table V below.

TABLE V Percent Mortality Compound No. 1 Day 2 Days 3 Days wherein R isa member selected from the group consisting of phenyl and lower alkylgroups of 1 to 3 carbon atoms, and X is a member selected from the groupconsisting of 9 fluorine and chlorine (2) mono and dialkali metal andmono and diamm'onium salts of the compounds of the said formula whereinall the X substituents are fluorine.

2. The method of claim 1 wherein soil containing weed seeds is contactedwith the toxic compound.

3. The method according to claim 1 wherein the toxic compound is1,3-bis(1,3-dichlorotetrafluoro-Z-hydroxy-2- propyl)-2-phenyl-1-propene.

4. The method according to claim 1 wherein the toxic compound isl,3-bis(hexafluoro-2-hydroxy-2-pr0pyl)-2- phenyl-l-propene.

5. The method according to claim 1 wherein the toxic compound is asodium salt of 1,3-bis(hexafluoro-2- hydroxy-2-propyl)-2-phenyl-1-propene.

6. The method according to claim 1 wherein the toxic 15 10 8. The methodaccording to claim 1 wherein the toxic compound is1,3-bis(1,3-dichlorotetrafluoro-Z-hydroxy)- Z-methyl-l-propene.

9. The method of claim 1 wherein growing weeds are contacted with thetoxic compound.

References Cited UNITED STATES PATENTS 3,320,047 5/1967 Gilbert et a1.71-122 3,324,187 6/1967 Litt et a1. 260633 3,393,993 7/1968 Gilbert eta1. 71-122 3,396,227 8/1968 Gilbert et a1. 71-122 FOREIGN PATENTS 10,0745/ 1965 Japan.

JAMES O. THOMAS, JR., Primary Examiner UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTION Patent No. 3, 9 9" Dated January 20, 1970Inventor(s) Everett E.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column in the Table, fourth column, "5. 5" should read Column 8, line 2,"compound" should read compounds line 11, "fllies" should read fliesClaim 1, that portion of the formula reading "H C-" should read HQC- Ill R=C R-C I l Column 9, line 16, should be inserted after "prooyl"SIGNED AND SEALED JUL? 1970 (SEAL) Arrest:

Attesting Officer Commissioner of Patents

